TW201632354A - Resin composition, prepreg using resin composition and laminate - Google Patents

Abstract

The invention provides a resin composition, prepreg using the resin composition and a laminate. The resin composition contains (A) a prepolymer of polyolefin resin and bifunctional maleimide or multifunctional maleimide and (B) vinyl thermosetting polyphenyl ether, wherein the weight of the vinyl thermosetting polyphenyl ether is 200-1,000 parts by weight on the basis that the weight of the prepolymer of the polyolefin resin and bifunctional maleimide or multifunctional maleimide is 100 parts by weight. According to the resin composition, the polyolefin resin and bifunctional maleimide or multifunctional maleimide are prepolymerized, so that the problem that bifunctional maleimide or multifunctional maleimide is incompatible with the polyolefin resin and the vinyl thermosetting polyphenyl ether is solved, a mixed glue solution is uniform and consistent, the appearance of the prepreg is uniform, and a base material resin region is free from a phase splitting problem.

Description

Resin composition and prepreg and laminate using same

The invention belongs to the technical field of copper clad laminates, and relates to a resin composition and a prepreg and a laminate using the same.

In recent years, with the development of electronic information technology, the miniaturization and high density of electronic equipment installations have increased the capacity and speed of information, and the heat resistance, water absorption, chemical resistance, mechanical properties, and dimensional stability of circuit boards have been stabilized. The comprehensive performance of properties such as properties and dielectric properties put forward higher requirements.

In terms of dielectric properties, in a high-speed circuit, the relationship between the signal transmission rate and the dielectric constant Dk of the insulating material is such that the lower the dielectric constant Dk of the insulating material, the faster the signal transmission rate. Therefore, in order to speed up the signal transmission rate, it is necessary to develop a substrate having a low dielectric constant. As the signal rate increases, the loss of signals in the substrate can no longer be ignored. The relationship between the signal loss and the rate, the dielectric constant Dk, and the dielectric loss factor Df is that the smaller the dielectric constant Dk of the substrate is, the smaller the dielectric loss factor Df is, and the smaller the signal loss is.

Therefore, the development of a high-speed circuit substrate having a low dielectric constant Dk and a low dielectric loss factor Df and good heat resistance has become a research and development direction that CCL manufacturers are paying attention to.

Polyphenylene ether resin contains a large amount of benzene ring structure in the molecular structure, and has no strong polar group. The group imparts excellent properties to the polyphenylene ether resin, such as high glass transition temperature, good dimensional stability, small linear expansion coefficient, low water absorption, especially excellent low dielectric constant and low dielectric loss, and is a high-speed preparation. An ideal resin material for circuit boards.

The butadiene-styrene copolymer does not contain a polar group, has good dielectric properties, low water absorption, and good flexibility. Butadiene-styrene copolymers contain reactive vinyl groups and are commonly used as crosslinkers in high speed electronic circuit substrate resin systems.

Maleimide has excellent heat resistance, flame retardancy, mechanical properties and dimensional stability, and is generally used as a crosslinking agent in high-speed electronic circuit substrate resin systems.

Maleimide has excellent heat resistance, flame retardancy, mechanical properties and dimensional stability, and is generally used as a crosslinking agent in high-speed electronic circuit substrate resin systems.

CN103965606A discloses a low dielectric material comprising: 40 to 80 parts by weight of polyphenylene ether; 5 to 30 parts by weight of bismaleimide; and 5 to 30 parts by weight of a polymer additive. Wherein, the structural formula of polyphenylene ether is as follows; The polymer additive is selected from the group consisting of polybutadiene, styrene-butadiene copolymer, styrene-butadiene-divinylbenzene copolymer, styrene-maleic anhydride copolymer, maleic anhydride polybutadiene Alkene, and combinations thereof. Since the styrene-butadiene copolymer, the polybutadiene, the styrene-butadiene copolymer-divinylbenzene copolymer, and the polyphenylene ether are incompatible with the maleimide, in the rubber mixing process There is a layering of the glue, and the appearance of the prepreg has a skin-like crack, and the phase of the resin in the base material has a problem of phase separation.

CN101643650A discloses a phosphorus-containing flame retardant applied to an electronic circuit base material. The phosphorus-containing flame retardant is added to a resin system of an unsaturated double bond, an engineering plastic or a polymer of a polyolefin to produce cross-linking and flame retarding effects. Among them, the unsaturated double bond resin includes butadiene, styrene, isoprene, divinylbenzene, toluene vinyl, acrylate, acrylonitrile, N-phenyl maleimide, N-vinyl a homopolymer or copolymer of phenylmaleimide, a vinyl-substituted polyphenylene ether, such as a copolymer of butadiene, styrene, and N-phenylmaleimide with a vinyl-substituted poly A phenyl ether resin composition, or a copolymer of butadiene, styrene, and N-vinylphenylmaleimide, and a vinyl-substituted polyphenylene ether resin composition for use in the production of an electronic circuit substrate. Since the maleimide used is a monomaleimide structure, the heat resistance of the substrate is lowered, and the coefficient of thermal expansion is large, compared to the bifunctional maleimide structure or the polyfunctional maleimide structure. The thermal stratification time is short and the thermal decomposition temperature is low.

CN101370866A discloses a resin composition which is a thermosetting resin composition of a semi-IPN type composite. The resin composition is derived from a prepolymer of a butadiene polymer and a crosslinking agent, and a semi-cured resin composition obtained by melting a polyphenylene ether phase. Wherein the butadiene polymer contains 40% or more of 1,2-butadiene units having 1,2-vinyl groups in the side chain in the molecule and is not chemically modified. In the invention, the polyphenylene ether-based thermoplastic polymer preferably has a molecular weight of 7,000 to 30,000. It can be seen from the examples that the thermoplastic polyphenylene ether of Japan Asahi Kasei Chemical Co., Ltd. is used, and the grade is S202A. Because thermoplastic polyphenylene ether is incompatible with butadiene polymers. In order to improve the compatibility between the two, the thermoplastic polyphenylene ether and the butadiene polymer are subjected to a compatibilization treatment. Since the thermoplastic polyphenylene ether and the butadiene polymer are not crosslinkable, a crosslinking agent such as maleimide is introduced to crosslink the butadiene polymer. A semi-IPN type uniform composite thermosetting resin composition in which a prepolymer of a butadiene polymer and a crosslinking agent is compatibilized with a polyphenylene ether to form an uncured polyphenylene ether-modified butadiene polymer. . In the case of homogenization (compatibilization) at this time, the polyphenylene ether and other components (the prepolymer of the butadiene polymer and the crosslinking agent) do not form a chemical bond, but the polyphenylene ether and the like A resin composition in which the component (the prepolymer of the butadiene polymer and the crosslinking agent) is physically entangled to form a microphase separation, and the appearance is uniformized (compatibilized). The structure of the IPN-type uniform composite thermosetting resin composition is as follows: Since the invention employs a thermoplastic polyphenylene ether and a butadiene polymer, there are the following problems: (1) The thermoplastic polyphenylene ether has a high molecular weight (the only polyphenylene ether used in the examples is the Japanese Asahi Kasei Chemical Company brand S202A). The thermoplastic polyphenylene ether has a number average molecular weight of 16,000), which results in high viscosity of the prepared glue, poor prepreg prepared (stripes, colloidal particles, dried flowers and bubbles); (2) due to the use Thermoplastic polyphenylene ethers do not contain vinyl reactive functional groups and cannot be crosslinked with butadiene polymers for curing. Therefore, compared with the thermosetting modified polyphenylene ether with vinyl group, the heat resistance is worse, resulting in insufficient heat resistance of the prepared electronic circuit substrate, and the prepared high-multilayer high-speed electronic circuit PCB has been subjected to many harsh conditions. After lead-free reflow soldering, significant heat resistance problems with layered bursts will occur.

WO 2013/110068 A1 discloses a resin composition comprising: a resin having a weight fraction of 30 to 80%, a base resin prepolymer, and the like; a component having a weight fraction of 1 to 30% containing at least a monofunctional group Maleidin, bifunctional maleimide, or single official A composition of maleimide and a bifunctional maleimide; a flame retardant; an initiator. In the invention, a resin prepolymer refers to a prepolymer of a polyolefin resin and a maleimide resin. The polyolefin resin is selected from the group consisting of polybutadiene, styrene-butadiene copolymer, polyisoprene, and styrene-butadiene-divinylbenzene copolymer. The maleic imine is at least one selected from the group consisting of a monofunctional maleimide, a difunctional maleimide or a monofunctional maleimide and a bifunctional maleimide. As is apparent from the description of the invention, the resin composition also includes a polyphenylene ether whose molecular chain end group structure is a phenylhydroxyl group, a methacrylate group or an acrylate group. The content of polyphenylene ether is 10 to 50% by weight of the entire glue. Therefore, in the resin composition, the main resin is a polyolefin, not a polyphenylene ether, resulting in insufficient heat resistance of the prepared electronic circuit substrate, and the prepared high-multilayer high-speed electronic circuit PCB has undergone many severe lead-free reflows. After welding, there will be significant heat resistance problems with the layered blasting plate.

In view of the problems of the prior art, one of the objects of the present invention is to provide a resin composition capable of satisfying the requirements for high-performance electronic circuit substrates for comprehensive properties such as dielectric properties and heat resistance.

In order to achieve the above object, the present invention employs the following technical means: a resin composition comprising: (A) a prepolymer of a polyolefin resin and a difunctional maleimide or a polyfunctional maleimide; a vinyl thermosetting polyphenylene ether; wherein the weight of the vinyl thermosetting polyphenylene ether is 100 parts by weight based on 100 parts by weight of the prepolymer of the polyolefin resin and the difunctional maleimide or polyfunctional maleimide 200 to 1000 parts by weight, for example, 250 parts by weight, 300 parts by weight, 350 parts by weight, 400 parts by weight, 450 parts by weight, 500 parts by weight, 550 parts by weight, 600 parts by weight, 650 parts by weight, 700 parts by weight, 750 parts by weight, 800 parts by weight, 850 parts by weight, 900 parts by weight or 950 parts by weight.

The weight ratio of the polyolefin resin to the prepolymer of the bifunctional maleimide or the polyfunctional maleimide is 100 parts by weight, and the weight of the vinyl thermosetting polyphenylene ether is 200 to 1000 parts by weight. The prepared plate has good heat resistance and dielectric properties.

In the above resin composition, the polyolefin resin is selected from any one or a mixture of at least two of a styrene-butadiene copolymer, a polybutadiene or a styrene-butadiene-divinylbenzene copolymer, and is ideal. The polyolefin resin described above is selected from the group consisting of amino-modified, maleic anhydride-modified, epoxy-modified, acrylate-modified, hydroxyl-modified or carboxyl-modified styrene-butadiene copolymers Any one or a mixture of at least two of polybutadiene, styrene-butadiene-divinylbenzene copolymer.

Exemplary polyolefin resins such as styrene-butadiene copolymer R100 of Sammeter, polybutadiene B-1000 of Japan's Soda, or styrene-butadiene-divinylbenzene copolymer R250 of Samtomer.

The weight of the difunctional maleimide or the polyfunctional maleimide is 10 to 100 parts by weight, for example, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50% by weight based on 100 parts by weight of the polyolefin resin. Parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight or 90 parts by weight.

The bifunctional maleimide or polyfunctional maleimide is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the polyolefin resin, so that the prepared plate has a good crosslinking density. And dielectric properties.

In the above resin composition, the structural formula of the difunctional maleimide or polyfunctional maleimide is as follows: R ₁₆ is a z-valent aliphatic or aromatic organic group; R ₁₇ and R ₁₈ are each independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, a substituted or unsubstituted C1. Any of -C8 branched alkyl groups; z represents an integer of 2 or more.

An exemplary bifunctional maleimide such as KI chemical is a bifunctional maleimide having the structural formula shown below: In the above resin composition, the prepolymerization reaction of the polyolefin resin and the prepolymer of the difunctional maleimide or the polyfunctional maleimide comprises the following steps: (1) the polyolefin resin is weakened by toluene or methyl ethyl ketone. The polar solvent is dissolved, and the bifunctional maleimide or polyfunctional maleimide is dissolved by a strong polar solvent such as N,N-dimethylformamide or N-methylpyrrolidone; (2) the polyolefin resin solution is used. Mix well with the bifunctional maleimide or polyfunctional maleimide solution, heat to the set temperature, then add the free radical initiator, prepolymerize for a certain time at the set temperature; monitor the bifunctional horse with GPC The conversion of the quinone imine or the polyfunctional maleimide, the conversion ratio of the bifunctional maleimide or the polyfunctional maleimide is 10-80%.

The radical initiator is selected from the group consisting of organic peroxide initiators, and further preferably selected from the group consisting of dilaurin peroxide, benzammonium peroxide, cumene peroxide, and neopentyl peroxide. Tert-butyl ester, pivalyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butylperoxy-3,5,5-trimethylhexanoate , tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butyl peroxidation Cyclohexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, peroxydicarbonate Tetraester, dip-pentyl peroxide, diisopropylbenzene peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butyl peroxide Hexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tetraamyl hydroperoxide, tert-butyl Hydrogen peroxide, t-butyl cumene peroxide, diisopropylbenzene hydroperoxide, peroxycarbonate-2- Tert-butyl ethylhexanoate, 2-ethylhexyl peroxybutyl carbonate, n-butyl 4,4-di(tert-butylperoxy)pentanoate, methyl ethyl ketone peroxide, perylene oxide Any one or a mixture of at least two.

In the resin composition, the structural formula of the vinyl thermosetting polyphenylene ether is as shown in the following formula (1): In the formula (1), a and b are independently an integer of 1 to 30, for example, 2, 5, 8, 11, 14, 17, 20, 23, 26 or 29, and Z is a formula (2) or (3) The structure shown, -(-OY-)-the structure shown in the formula (4), -(-OXO-)-the structure shown in the formula (5): (2)

In the formula (3), the A-based aromatic group, the carbonyl group or the alkylene group having 1 to 10 (e.g., 2, 3, 4, 5, 6, 7, 8, or 9) carbon atoms, m is 0 to 10 ( For example, an integer of ₁ , ₂ , 3, 4, 5, 6, 7, 8, or 9), R ₁ , R ₂ and R _{3 are the} same or different and are independently hydrogen or an alkyl group having 10 or less carbon atoms; In the formula (4), R ₄ and R _{6 are the} same or different and each independently is a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms, and R ₅ and R _{7 are the} same or different. , independently, a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms; In the formula (5), R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R ₁₅ are the same or different and independently represent a hydrogen atom, a halogen atom or a carbon atom of 8 or less. An alkyl group or a phenyl group having 8 or less carbon atoms, and B is an alkylene group, -O-, -CO-, -SO-, -SC-, -SO ₂ - or -C(CH ₃ ) ₂ -, n-system 0 Or 1.

Exemplary vinyl thermosetting polyphenylene ethers such as Sabic's methacrylate-based modified polyphenylene ether MX9000, Mitsubishi Chemical's styryl-modified polyphenylene ether St-PPE-1.

Preferably, the vinyl thermosetting polyphenylene ether has a number average molecular weight of 500 to 10,000 g/mol, more preferably 800 to 8000 g/mol, still more preferably 1,000 to 7,000 g/mol.

Preferably, the resin composition further comprises a component (C) initiator. The initiator is a radical initiator, and the radical initiator is selected from the group consisting of organic peroxide initiators, and further preferably selected from the group consisting of dilaurin peroxide, benzoic acid peroxide, and neopentosyl peroxide. Propyl phenyl ester, tert-butyl peroxy neopentate, pivalyl peroxypivalate, tert-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy-3,5 , 5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1 , 1-di-tert-butylperoxycyclohexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, peroxydicarbonate Hexaester, tetradecyl peroxydicarbonate, dip-pentyl peroxide, diisopropylbenzene peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2 , 5-di-tert-butylperoxyhexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tetramethyl Hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzene, dicumyl Hydrogen peroxide, tert-butyl peroxycarbonate-2-ethylhexanoate, 2-ethylhexyl t-butyl peroxycarbonate, n-butyl 4,4-di(tert-butylperoxy)pentanoate Any one or a mixture of at least two of methyl ethyl ketone peroxide, peroxy hexane.

The weight of the initiator is 100 parts by weight based on the weight of the prepolymer of the polyolefin resin and the difunctional maleimide or polyfunctional maleimide, the vinyl thermosetting polyphenylene ether, and the initiator. ~3 parts by weight, for example, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, 2.0 parts by weight, 2.2 parts by weight, 2.4 parts by weight, 2.6 parts by weight or 2.8 parts by weight.

Preferably, the resin composition further comprises a component (D) flame retardant, which is a bromine-containing flame retardant or/and a phosphorus-containing flame retardant.

In the above resin composition, the flame retardant is a phosphorus-containing flame retardant containing a DOPO structure, and its molecular structural formula is as follows: Wherein n is an integer from 0 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, or 9.

An exemplary phosphorus-containing flame retardant containing a DOPO structure is a phosphorus-containing flame retardant XP-7866 from Albemarle, USA.

The weight of the flame retardant is 0 to 40 based on 100 parts by weight of the prepolymer of the polyolefin resin and the bifunctional maleimide or polyfunctional maleimide, the vinyl thermosetting polyphenylene ether and the initiator. Parts by weight, for example, 3 parts by weight, 6 parts by weight, 9 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 21 parts by weight, 24 parts by weight, 27 parts by weight, 30 parts by weight, 33 parts by weight, 36 parts by weight Parts or 39 parts by weight.

Preferably, the resin composition further comprises a component (E) filler selected from the group consisting of crystalline cerium oxide, amorphous cerium oxide, spherical cerium oxide, titanium dioxide, cerium carbide, glass fiber, oxidation. Any one or a mixture of at least two of aluminum, aluminum nitride, boron nitride, barium titanate or barium titanate.

Filled with 100 parts by weight of the weight of the polyolefin resin and the difunctional maleimide or polyfunctional maleimide prepolymer, vinyl thermosetting polyphenylene ether, initiator and flame retardant The weight of the material is 0 to 150 parts by weight, for example, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight. 110 parts by weight, 120 parts by weight, 130 parts by weight or 140 parts by weight.

The term "comprising" as used in the present invention means that in addition to the components, other components may be included, and such other components impart different characteristics to the resin composition. In addition, the "including" as used in the present invention may also be replaced by a closed "for" or "consisting of".

For example, the resin composition may contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These various additives may be used singly or in combination of two or more.

Further, the present invention provides a prepreg produced by using the above resin composition, comprising a substrate and a resin composition as described above which is adhered to the substrate by impregnation and drying.

Further, the present invention also provides a laminate produced using the above resin composition, comprising a plurality of laminated prepregs.

Further, the present invention also provides a copper-clad laminate produced using the above resin composition, comprising a plurality of laminated prepregs and a copper foil which is laminated on one or both sides of the laminated prepreg.

Further, the present invention also provides a printed circuit board produced using the above resin composition, comprising a plurality of laminated prepregs.

The preparation of the high-speed electronic circuit substrate by the above formula comprises the following steps: (1) prepolymerizing the polyolefin resin with a bifunctional maleimide or a polyfunctional maleimide in the presence of a radical initiator, The conversion rate of bismaleimide or polymaleimide is determined by GPC, the conversion range is controlled by 10-80%, and the weight of polyolefin resin is 100 weight. The weight of the difunctional maleimide or polyfunctional maleimide is 10-100 parts by weight; (2) weighing the resin composition: using a polyolefin resin and a bifunctional maleimide or more The weight of the copolymer of maleic imine is 100 to 1000 parts by weight based on 100 parts by weight of the thermosetting polyphenylene ether; the polyolefin resin and the bifunctional maleimide or the multifunctional Malayan The weight of the amine prepolymer, the vinyl thermosetting polyphenylene ether and the initiator is 100 parts by weight, the weight of the initiator is 1 to 3 parts by weight, and the weight of the flame retardant is 0 to 40 parts by weight; The weight of the difunctional maleimide or polyfunctional maleimide prepolymer, vinyl thermosetting polyphenylene ether, initiator and flame retardant is 100 parts by weight, and the weight of the filler is 0 to 150 parts by weight. (3) a polyolefin resin mixed with a prepolymer of a difunctional maleimide or a polyfunctional maleimide, a vinyl thermosetting polyphenylene ether, an optional initiator, an optional filler, and optionally a flame retardant And adding an appropriate amount of solvent, stirring and dispersing evenly, so that the filler and the flame retardant are uniformly dispersed in the glue. Infiltrating the glass fiber cloth with the prepared glue liquid, and drying the film in an oven at a suitable temperature for a certain period of time to remove the solvent to form a prepreg; (4) aligning several prepregs neatly, with copper foil on top and bottom, The laminate was cured in a press to obtain a copper clad laminate.

In contrast to the prior art, the present invention has the following effects: (1) The present invention utilizes a polyolefin resin to prepolymerize with a bifunctional maleimide or a polyfunctional maleimide to solve the bifunctional Malayan The incompatibility between the amine or polyfunctional maleimide and the polyolefin resin and the vinyl thermosetting polyphenylene ether is uniform, the mixed glue solution is uniform, the appearance of the prepreg is uniform, and the substrate resin region has no phase separation problem; (2) The maleidanilide used in the present invention is a bifunctional maleimide or a polyfunctional maleimide, and the prepared substrate has higher heat resistance than the monofunctional maleimide. Thermal expansion system Smaller number, longer thermal stratification time and higher thermal decomposition temperature; (3) Vinyl thermosetting polyphenylene ether can be mixed with polyolefin resin, bismaleimide or doraminide The reaction forms a three-dimensional crosslinked network structure, and the prepared high-speed electronic circuit substrate has better heat resistance than the thermoplastic polyphenylene ether containing no vinyl reactive group, such as higher glass transition temperature and higher thermal expansion coefficient. Small and hot stratification time is longer; (4) using vinyl thermosetting polyphenylene ether as main resin, polyolefin resin and difunctional maleimide or polyfunctional maleimide prepolymer as crosslinker Compared with the polyolefin resin as the main resin system, the prepared substrate has better heat resistance.

The technical means of the present invention will be further described below by way of specific embodiments.

The raw materials selected for preparing the high-speed electronic circuit substrate according to the examples and comparative examples of the present invention are shown in Table 1 below:

1. Prepolymerization of polyolefin resin with difunctional maleimide or polyfunctional maleimide

1. Prepolymerization Example 1

25 g of styrene-butadiene copolymer R100 was weighed and dissolved in 25 g of toluene solvent. 5 g of K-I chemical difunctional maleimide was weighed and dissolved in 20 g of N,N-dimethylformamide solvent. The dissolved styrene-butadiene copolymer R100 solution and K-I chemical difunctional maleimide solution were mixed and stirred uniformly. The mixed solution was heated to 120 ° C, and 0.1 g of DCP dissolved in 10 g of toluene was added and reacted for 1.5 hours. Stop heating and cool for use.

2. Pre-polymerization example 2

25 g of polybutadiene B-1000 was weighed and dissolved in 25 g of toluene solvent. 5 g of K-I chemical difunctional maleimide was weighed and dissolved in 20 g of N,N-dimethylformamide solvent. The dissolved styrene-butadiene copolymer R100 solution and K-I chemical difunctional maleimide solution were mixed and stirred uniformly. The mixed solution was heated to 120 ° C, and 0.1 g of DCP dissolved in 10 g of toluene was added and reacted for 1.5 hours. Stop heating and cool for use.

3. Prepolymerization Example 3

25 g of styrene-butadiene-divinylbenzene copolymer R250 was weighed and dissolved in 25 g of toluene solvent. 5 g of K-I chemical difunctional maleimide was weighed and dissolved in 20 g of N,N-dimethylformamide solvent. The dissolved styrene-butadiene copolymer R100 solution and K-I chemical difunctional maleimide solution were mixed and stirred uniformly. The mixed solution was heated to 120 ° C, and 0.1 g of DCP dissolved in 10 g of toluene was added and reacted for 1.5 hours. Stop heating and cool for use.

4. Prepolymerization Example 4

25 g of styrene-butadiene copolymer R250 was weighed and dissolved in 25 g of toluene solvent. 5 g of Jinyi Chemical's trifunctional maleimide was weighed and dissolved in 20 g of N,N-dimethylformamide solvent. The dissolved styrene-butadiene copolymer R100 solution and Jinyi Chemical's trifunctional maleic imine solution were mixed and stirred uniformly. The mixed solution was heated to 120 ° C, and 0.1 g of DCP dissolved in 10 g of toluene was added and reacted for 1.5 hours. Stop heating and cool for use.

Second, the preparation of high-speed electronic circuit substrate

1. Embodiment 1

25 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of KI chemical difunctional maleimine prepared by prepolymerization, 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of the curing initiator DCP and 30 g parts by weight of the bromine-containing flame retardant BT-93W were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be suitable for single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

2. Embodiment 2

Prepolymer prepared by prepolymerization of 25 g parts by weight of polybutadiene B-1000 and 5 g parts by weight of KI chemical of difunctional maleic imine, 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 weight The curing initiator DCP, 30 g parts by weight of the bromine-containing flame retardant BT-93W, and 50 g of the molten cerium fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be suitable for single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 bonded sheet adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1OZ thickness, vacuum laminated for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

3. Embodiment 3

25 g parts by weight of styrene-butadiene-divinylbenzene copolymer R250 and 5 g parts by weight of KI chemical difunctional maleimine prepared by prepolymerization, 70 g parts by weight of vinyl thermosetting Polyphenylene ether MX9000, 3.0 parts by weight of curing initiator DCP, 30 g parts by weight of bromine-containing flame retardant BT-93W, and 50 g of molten cerium fine powder 525 were dissolved in toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

4. Example 4

25 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of Jinyi Chemical's trifunctional maleic imine prepared by prepolymerization, 70 g parts by weight of vinyl thermosetting polyphenylene ether St - PPE-1, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93W, and 50 g of a molten fine powder 525, dissolved in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

5. Example 5

25 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of KI chemical difunctional maleimine prepared by prepolymerization, 70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator BPO, 30 g parts by weight of a phosphorus-containing flame retardant XP-7866, and 50 g of a molten fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. Physical properties are shown in Table 2.

6. Example 6

25 g parts by weight of styrene-butadiene copolymer R100 and 2.5 g parts by weight of KI chemical of difunctional maleic imine prepared by prepolymerization of prepolymer, 55 g parts by weight of vinyl thermosetting polyphenylene ether MX9000 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93W, and 50 g of a molten fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

7. Example 7

25 g parts by weight of styrene-butadiene copolymer R100 and 25 g parts by weight of KI chemical difunctional maleimine prepared by prepolymerization, 100 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93W, and 50 g of a molten fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum-laminated for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

8. Example 8

25 g parts by weight of styrene-butadiene copolymer R100 and 2.5 g parts by weight of KI chemical of difunctional maleic imine prepared by prepolymerization of prepolymer, 275 g parts by weight of vinyl thermosetting polyphenylene ether St - PPE-1, 3.0 parts by weight of a curing initiator DCP, 60 parts by weight of a bromine-containing flame retardant BT-93W, and 100 g of a molten fine powder 525, dissolved in a toluene solvent, and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

9. Example 9

25 g parts by weight of styrene-butadiene copolymer R100 and 25 g parts by weight of KI chemical of difunctional maleic imine prepared by prepolymerization of prepolymer, 500 g parts by weight of vinyl thermosetting polyphenylene ether St- PPE-1, 3.0 parts by weight of a curing initiator DCP, 90 g parts by weight of a bromine-containing flame retardant BT-93W, and 150 g of a molten fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 3.

10. Comparative Example 1

70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000 dissolved in toluene, 5 g parts by weight of N,N-dimethylformamide, KI chemical difunctional maleimide, 25 g parts by weight The diene-styrene copolymer R100, 3.0 parts by weight of a curing initiator DCP, 30 g parts by weight of a bromine-containing flame retardant BT-93W, and 50 g of a molten fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 4.

11. Comparative Example 2

70 g parts by weight of vinyl thermosetting polyphenylene ether MX9000 dissolved in toluene, 5 g parts by weight of N,N-dimethylformamide, monofunctional maleimide of Wuhan Zhiyi Technology, 25 g parts by weight Butadiene-styrene copolymer R100, 3.0 parts by weight of curing initiator DCP, 30 g parts by weight of bromine-containing flame retardant BT-93W, 50 g of molten cerium fine powder 525, dissolved in toluene solvent, and adjusted to suit Viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 4.

12. Comparative Example 3

70 g parts by weight of thermoplastic polyphenylene ether S202A dissolved in toluene, 25 g parts by weight of butadiene polymer B-1000 dissolved in toluene, dissolved in 5 g parts by weight of N,N-dimethylformamide The chemical bifunctional maleimide is mixed and stirred evenly. Then the temperature was raised to 120 ° C, and 0.1 g of toluene was added. DCP, reaction for 1.5 hours. Stop heating and cool for use.

The above-mentioned semi-IPN type composite thermosetting resin composition, 3.0 parts by weight of curing initiator DCP, 30 g parts by weight of bromine-containing flame retardant BT-93W, and 50 g of molten cerium fine powder 525 were dissolved in toluene solvent and adjusted to Suitable for viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 4.

13. Comparative Example 4

70 g parts by weight of styrene-butadiene copolymer R100 and 5 g parts by weight of KI chemical difunctional maleimine prepared by prepolymerization, 25 g parts by weight of vinyl thermosetting polyphenylene ether MX9000, 3.0 parts by weight of the curing initiator DCP, 30 g parts by weight of the bromine-containing flame retardant BT-93W, and 50 g of the molten fine powder 525 were dissolved in a toluene solvent and adjusted to a suitable viscosity. The 2116 glass fiber cloth was used to infiltrate the glue, and the clamp shaft was controlled to be a single weight, and the sheet was baked in an oven to remove the toluene solvent to obtain a 2116 adhesive sheet. Four sheets of 2116 bonded sheets were overlapped, and the upper and lower sides were coated with a copper foil of 1 OZ thickness, vacuum laminated and cured for 90 minutes in a press, a curing pressure of 50 kg/cm ² , and a curing temperature of 200 ° C to obtain a high-speed electronic circuit substrate. The physical properties are shown in Table 4.

Physical property analysis:

From Table 2 and Table 3, it is known that vinyl thermosetting polyphenylene ether, polyolefin resin and malayan are solved by prepolymerization of polyolefin resin with difunctional maleimide or polyfunctional maleimide. The problem of imine incompatibility, the prepared prepreg has a good appearance, and the resin region of the substrate has no resin phase separation. Polyolefin resin, vinyl thermosetting polyphenylene ether and maleimide can be cross-linked and cured to form a three-dimensional network structure with high crosslink density. The vinyl thermosetting polyphenylene ether is used as the main resin to ensure excellent heat resistance of the prepared electronic circuit substrate. The prepared substrate has excellent properties such as excellent dielectric properties and heat resistance, and is completely suitable for substrates for high-speed electronic circuit PCBs.

From Comparative Example 1, the styrene-butadiene copolymer and the difunctional maleimide are known. Without pre-polymerization, the appearance of the prepreg is poor, there are crack defects, and the resin region of the substrate has a phase separation problem.

It can be seen from Comparative Example 2 that the use of a monofunctional maleimide and no prepolymerization with the styrene-butadiene copolymer results in poor appearance of the prepreg, cracking defects, and phase separation of the substrate resin region. problem. In addition, compared with bismaleimide, the heat resistance is worse (the glass transition temperature is lower, the thermal decomposition temperature is lower, the thermal stratification time is shorter, and the thermal expansion coefficient is larger).

It can be seen from Comparative Example 3 that the electronic circuit substrate prepared by the compatibilization process using the thermoplastic polyphenylene ether and the polybutadiene results in insufficient heat resistance of the prepared electronic circuit substrate (lower glass transition temperature, thermal decomposition) The temperature is lower, the thermal stratification time is shorter, and the thermal expansion coefficient is larger. Further, the PCB for the high-multilayer high-speed electronic circuit prepared has a large heat resistance problem of the layered blasting plate after many severe lead-free reflow soldering. Moreover, due to the large molecular weight of the thermoplastic polyphenylene ether, the appearance of the prepreg is streaked, colloidal and dry flower, and the phase of the resin in the substrate is microphase separated.

As is apparent from Comparative Example 4, the polyolefin resin (the styrene-butadiene copolymer of this example) was used as the host resin instead of the polyphenylene ether as the main resin, resulting in insufficient heat resistance of the prepared electronic circuit substrate (glass The lower the transformation temperature, the lower the thermal decomposition temperature, the shorter the thermal delamination time, and the larger the thermal expansion coefficient. The PCB for the high-multilayer high-speed electronic circuit prepared is delaminated after many times of harsh lead-free reflow soldering. A major heat resistance problem.

The embodiments of the invention are not intended to limit the invention. Equivalent changes and modifications of the present invention in accordance with the technical idea of the present invention are still within the scope of the present invention.

The Applicant declares that the present invention is described in detail by the above embodiments, but the present invention is not limited to the above detailed methods, that is, the present invention is not intended to be The fine method was implemented. It is to be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the various materials of the present invention, and the addition of the auxiliary components, and the manner of the specific methods are all within the scope of the present invention.

Claims (26)

A resin composition characterized in that the resin composition comprises: (A) a prepolymer of a polyolefin resin with a bifunctional maleimide or a polyfunctional maleimide; (B) a vinyl thermosetting polyphenylene An ether; wherein the weight of the vinyl thermosetting polyphenylene ether is 200 to 1000 parts by weight based on 100 parts by weight of the prepolymer of the polyolefin resin and the bifunctional maleimide or the polyfunctional maleimide . The resin composition according to claim 1, wherein the polyolefin resin is selected from the group consisting of styrene-butadiene copolymer, polybutadiene or styrene-butadiene-divinylbenzene copolymer. Any one or a mixture of at least two. The resin composition according to claim 2, wherein the polyolefin resin is selected from the group consisting of amino-modified, maleic anhydride-modified, epoxy-modified, acrylate-modified, hydroxyl groups. Any one or a mixture of at least two of a modified or carboxyl modified styrene-butadiene copolymer, polybutadiene, styrene-butadiene-divinylbenzene copolymer. The resin composition according to the first aspect of the invention, wherein the weight of the bifunctional maleimide or the polyfunctional maleimide is 10 to 100 by weight based on 100 parts by weight of the polyolefin resin. Share. The resin composition as described in claim 1, wherein the bifunctional maleimide or polyfunctional maleimide has the structural formula: R ₁₆ is a z-valent aliphatic or aromatic organic group; R ₁₇ and R ₁₈ are each independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-C8 linear alkyl group, substituted or unsubstituted. Any one of C1-C8 branched alkyl groups; z represents an integer of 2 or more. The resin composition according to claim 5, wherein the difunctional maleimide has the structure shown below: The resin composition according to claim 5, wherein the polyfunctional maleimide has the structure shown below: The resin composition according to claim 1, wherein the vinyl thermosetting polyphenylene ether has the following structural formula: (1): In the formula (1), a and b are independently an integer of 1 to 30, a structure represented by the Z system (2) or (3), and a structure represented by the formula (4), (-OY-)- -(-OXO-)-the structure shown in the formula (5): In the formula (3), the A-based aromatic group, the carbonyl group or the alkyl group having 1 to 10 carbon atoms, m is an integer of 0 to 10, and R ₁ , R ₂ and R _{3 are} independently hydrogen or a carbon number. An alkyl group of 10 or less; In the formula (4), R ₄ and R _{6 are each} independently a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms, and R ₅ and R _{7 are} independently a hydrogen atom or a halogen. An atom, an alkyl group having 8 or less carbon atoms or a phenyl group having 8 or less carbon atoms; In the formula (5), R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ and R _{15 are} independently a hydrogen atom, a halogen atom, an alkyl group having 8 or less carbon atoms or a carbon number. a phenyl group of 8 or less, a B-alkylene group, -O-, -CO-, -SO-, -SC-, -SO ₂ - or -C(CH ₃ ) ₂ -, n is 0 or 1. The resin composition according to claim 8, wherein the vinyl thermosetting polyphenylene ether has a number average molecular weight of 500 to 10,000 g/mol. The resin composition according to claim 9, wherein the vinyl thermosetting polyphenylene ether has a number average molecular weight of 800 to 8000 g/mol. The resin composition according to claim 10, wherein the vinyl thermosetting polyphenylene ether has a number average molecular weight of 1,000 to 7,000 g/mol. The resin composition as described in claim 1, wherein the resin composition further comprises a component (C) initiator. The resin composition according to claim 12, wherein the initiator is a radical initiator, and the radical initiator is selected from the group consisting of organic peroxide initiators. The resin composition according to claim 13, wherein the radical initiator is selected from the group consisting of dilaurin peroxide, benzammonium peroxide, cumene peroxide, and peroxidation. New tert-butyl sulphate, pivalyl peroxypivalate, tert-butyl peroxypivalate, tert-butyl peroxyisobutyrate, tert-butylperoxy-3,5,5-trimethyl Caproic acid ester, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, 1,1-di-tert-butylperoxy-3,5,5-trimethylcyclohexane, 1,1-di-tert-butyl Base oxycyclohexane, 2,2-di(tert-butylperoxy)butane, bis(4-tert-butylcyclohexyl)peroxydicarbonate, hexadecyl peroxydicarbonate, peroxide Carbonate tetradecyl ester, dip-pentyl peroxide, diisopropylbenzene peroxide, bis(tert-butylperoxyisopropyl)benzene, 2,5-dimethyl-2,5-di-tert-butyl Base oxidized hexane, 2,5-dimethyl-2,5-di-tert-butylperoxyhexyne, diisopropylbenzene hydroperoxide, cumene hydroperoxide, tetraamyl hydroperoxide, uncle Butyl hydrogen peroxide, t-butyl peroxy cumene, diisopropylbenzene hydroperoxide, peroxygen Tert-butyl carbonate-2-ethylhexanoate, 2-ethylhexyl t-butyl peroxycarbonate, n-butyl 4,4-di(tert-butylperoxy)pentanoate, methyl ethyl ketone peroxide, Oxidation of any one or a mixture of at least two of hexanes. The resin composition according to claim 12, wherein the polyolefin resin is a prepolymer of a difunctional maleimide or a polyfunctional maleimide, a vinyl thermosetting polyphenylene ether, and an initiator. The weight of the initiator is 100 parts by weight, and the weight of the initiator is 1 to 3 parts by weight. The resin composition according to claim 12, wherein the resin composition further comprises a component (D) flame retardant. The resin composition according to claim 16, wherein the flame retardant is a bromine-containing flame retardant or/and a phosphorus-containing flame retardant. The resin composition according to claim 17, wherein the flame retardant is a phosphorus-containing flame retardant containing a DOPO structure, and the molecular structural formula thereof is as follows: Wherein n is an integer from 0 to 10. The resin composition according to claim 16, wherein the prepolymer of a polyolefin resin and a difunctional maleimide or a polyfunctional maleimide, a vinyl thermosetting polyphenylene ether, and an initiator are used. The weight of the flame retardant is 0 to 40 parts by weight based on 100 parts by weight. The resin composition according to claim 16, wherein the resin composition further comprises a component (E) filler. The resin composition according to claim 20, wherein the filler is selected from the group consisting of crystalline cerium oxide, amorphous cerium oxide, spherical cerium oxide, titanium dioxide, cerium carbide, glass fiber, alumina, Any one or at least one of aluminum nitride, boron nitride, barium titanate or barium titanate a mixture of the two. The resin composition according to claim 20, wherein the prepolymer of a polyolefin resin and a bifunctional maleimide or a polyfunctional maleimide, a vinyl thermosetting polyphenylene ether, an initiator And the weight of the flame retardant is 100 parts by weight, and the weight of the filler is 0 to 150 parts by weight. A prepreg characterized in that it comprises a substrate and a resin composition as described in any one of claims 1 to 22, which is adhered to the substrate by impregnation and drying. A laminate characterized by comprising at least one prepreg as recited in claim 23 of the above-mentioned application. A copper clad laminate characterized by comprising at least one prepreg as disclosed in claim 23 and a copper foil laminated on one or both sides of the laminated prepreg. A printed circuit board characterized by comprising at least one prepreg as disclosed in claim 23 of the above-mentioned application.